Electron spin measurement device and measurement method

ABSTRACT

An electron spin measuring device of the organic thin film element is provided with: at least one sample tube into which a sample for measurement is inserted and which is sealed together with specific gas or with vacuum; a cavity into which the at least one sample tube is inserted; an electric characteristic measuring device for the characteristic evaluation of the organic thin film element which is the sample; connected wiring for interconnecting the electrical characteristic measuring device and the sample for measurement in the sample tube; and a light receiving/emitting device for performing the light irradiation to the sample for measurement, and/or performing the detection of the light emission from the organic thin film element, wherein the cavity resonator irradiates microwaves having the number of vibration corresponding to the Zeeman energy splitting of the unpaired electron, sweeps a magnetic field to the sample tube, and measures the transition between the energy levels caused by the reversal of the direction of the electron spin.

TECHNICAL FIELD

The present invention relates to an electron spin measuring device and measuring method in order to improve the characteristics of thin film device.

BACKGROUND ART

The research about the electronic applications of organic thin film devices is needed in recent these years such as field-effect transistor (FETs), electroluminescent (EL) diodes, solar batteries.

A FETs have attracted much attention because the gain of the FET is advantage characteristic over the amorphous silicon FET. EL diodes are currently used in full color display because of advantage characteristic, such as self radiation and high luminance, over liquid crystal display.

Ordinary measurement method of organic molecular device was electrical conductivity function measurement method, or crystal structure analysis method by X ray.

Typical X ray method is X ray diffraction method that use the phenomenon that X ray is diffracted by crystal lattice.

X ray is very short electromagnetic wave. The X ray diffraction method is the method that atomic arrangement is analyzed by the diffraction data.

However, X ray reach only several hundred μm from the surface of macro big molecular electronic device. So the X ray diffraction method is the method that is restricted to analysis of the surface of crystal structure of material.

To conclude, it is difficult to observe charge carriers and to analysis electrical conductivity on the face of boundary between organic and insulator, by conventional macro analysis method.

As micro analysis method, making direct an observation spin of unpaired electron in paramagnetic material. Electron has spin angular momentum and magnetic momentum. In case paramagnetic material in magnetic field, the energy level of unpaired electron is changed to two levels.

Using these phenomena, observing the electron spin resonance that is the absorption of microwave by unpaired electron transition in sample device that uses material that poses unpaired electron, in several thousand gauss magnetic field.

Thus, the observation of the unpaired electrons' spin states is possible, because charge carrier in the material is as static as possible. There are the observation reports of the organic field effect devices that pose insulator by which charge carrier can be trapped. For example, as for MIS (Metal Insulator Semiconductor) surface, TFT (Thin Film Transistor) surface.

By the micro analysis of observation of electron spin state, the molecular aggregation structures and electronic states of field-effect doped charge carriers into the polymers in a device are clarified.

Inventor observed directly the electron spin of charge carriers which exist in MIS surface or FET surface in the organic thin film devices that contains insulated film, and analyzed and reported these results (See Non-patent document 1 to Non-patent document 3).

However, it is difficult to observe the accumulation of electron spin of charge carriers in organic thin film solar battery that does not contain insulated film. Furthermore, an organic thin film solar battery needs irradiation of light.

I cannot find the report about evaluation of the electron spin of charge carriers in organic thin film solar battery. As for application of electron spin resonance, the method of measuring the deterring of organic material which is used for automobile body painting is reported (see Patent document 1). As for application of electron spin resonance while developing an organic EL device, there is an example about evaluation of the substrate for the organic electroluminescent. The element is composed of a base material, an electrode layer formed on the base material in patterned-form, and a photo-catalyst-containing layer formed so as to cover the electrode layer, containing photo-catalyst and binder, changing its wettability by an action of the photo-catalyst by energy irradiation. In this case, electron spin resonance spectrum is measured while irradiating ultraviolet-ray on the photo-catalyst-containing layer (see Patent document 2).

There is also an example of organic thin-film solar cell as follow, to provide an organic thin-film solar cell, having a hole extraction layer and exhibiting high photoelectric conversion efficiency. The organic thin film solar cell comprises a substrate, a first electrode layer formed on the substrate, a hole extraction layer formed on the first electrode layer, a photoelectric conversion layer formed on the hole extraction layer, and a second electrode layer formed on the photoelectric conversion layer, wherein the hole extraction layer contains a conductive polymer material and a low molecular weight compound with an unpaired electron (see Patent document 4).

There is also the publication of application as for method and device for measuring of time-resolved electron spin resonance. In the publication, two sets of sample chambers comprising a sample and a cavity resonator are used, one sample chamber (a main sample chamber) is placed inside a magnetic field, and the other sample chamber (a reference sample chamber) is placed outside the magnetic field.

There is another publication of application as for organic thin film solar cell element and coating liquid for forming photoelectric conversion layer (see Patent document 5).

-   Patent document 1: Japanese Unexamined Patent Application     Publication No. H9-038078 -   Patent document 2: Japanese Unexamined Patent Application     Publication No. 2007-48529 -   Patent document 3: Japanese Unexamined Patent Application     Publication No. 2006-278584 -   Patent document 4: Japanese Unexamined Patent Application     Publication No. 2002-257759 -   Patent document 5: Japanese Unexamined Patent Application     Publication No. 2008-91467 -   Non-Patent Document 1: K. Marumoto et al. “Electron Spin Resonance     of Field Induced Polarons in Regioregular Poly(3-allylthiophene)     Using Metal Insulator Semiconductor Diode Structures”, Journal of     the Physical Society of Japan 74(11) (2005) 3066-3076 -   Non-Patent Document 2: K. Marumoto et al. “Spatial Extent of Wave     Functions of Gate Induced Hole Carriers in Pentacene Field Effect     Devices as Investigated by Electron Spin Resonance”, Physical Review     Letters 97(25) (2006) 256603-1-256603-4 -   Non-Patent Document 3: K. Marumoto et al. “Electron Spin Resonance     Observation of Gate Induced Ambipolar Charge Carriers in Organic     Devices”, Japanese Journal of Applied Physics 46(48) (2007)     L1191-L1193

DISCLOSURE OF THE INVENTION Objects of the Invention

The research and development for improvement of organic thin film device must start from understanding the charge carrier states and elucidation of the essential conduction function in the organic layer. For the purpose, the micro evaluation that in actual using condition of organic thin film device, directly measuring accumulated charge carriers in organic layer, is essential. For the purpose, direct measurement of the charge carrier in organic thin film solar battery is effective.

However, I cannot find the document about the example of the micro evaluation about organic thin film devices.

Therefore, for the purpose of characteristic improvement of device, the method and device about measuring the spin resonance phenomenon of the charge carrier while receiving light irradiation have been expected.

SUMMARY OF THE INVENTION

This invention is related to electron spin measuring device which is used for evaluating organic thin film device. The electron spin measuring device comprises a tube in which test sample is inserted, the cavity in which the tube is inserted, electric measuring device of the organic thin film device, the wire that is connected the test sample and the electric measuring device, light emitting and measuring light device that irradiates light to the sample and or measure light from the organic thin film device, the electron spin measuring monitors for observing the absorption as the field is changed, while irradiating the micro wave in which contain Zeeman energy division frequency, to the cavity, and measuring the energy level transition that occurs when the electron spin direction is reversed.

FIG. 2 is a sample for measurement (120) for carrying out of this invention. On substrate (50), organic thin film layers (52), is sat between negative electrode plate (54) and positive electrode plate (58). For driving the organic thin film layers (52) from outside this invention measuring device, the negative electrodes plate (54) is connected to the electric characteristic measuring device (310) by wirings (60). Another positive electrode plate (58) is connected to earth by wire (64). The material of wire (64) and the wirings (60) shall be non magnetic or weak magnetic. The influence, between unpaired electron spin and organic thin film device, should be avoided. The sample size of organic thin film device is better as large as possible to enter sample tube (100). Actual sample size of organic thin film device which I used is the length L is about 30 mm, the width W is 3 mm and the height is less than about 1 mm.

FIG. 3 is a sample for measurement (120) in the sample tube (100) of the electron spin measuring device (1) for carrying out this invention. The sample for measurement (120) is set in the sample tube (100), the thin connected wiring (130) are took out for connecting to joining terminal (140) which are connected to the electric characteristic measuring device (310).

A technical range of this invention is not limited within the range described in the execution form though it explained by using the execution form of this invention. In the execution form, various change or improvements can be added. It is clear that the form that adds such a change or the improvement can be included within the technical range of this invention, too from the description of the claim.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a block diagram of a preferred mode for carrying out this invention.

FIG. 2 is a measurement sample for carrying out this invention.

FIG. 3 is a measurement sample in the tube for carrying out this invention.

FIG. 4 is the example of a measurement sample in the tube for carrying out this invention.

FIG. 5 is the measurement ESR signal data by the spin electron spin measurement device of this invention when the voltage on the sample device is changed.

FIG. 6 is the measurement ESR signal data by the spin electron spin measurement device of this invention when the light irradiating time on the sample device is changed.

FIG. 7 is a block diagram of another preferred mode for carrying out this invention.

FIG. 8 is a measurement sample in the tube that is axially transferable for another preferred mode carrying out this invention.

FIG. 9 is the tube that magnetic field or light irradiation to the sample is rotatable for another preferred mode carrying out this invention.

FIG. 10 is the tube that the magnetic field is perpendicular to the sample for another preferred mode carrying out this invention.

FIG. 11 is the tube that the magnetic field is parallel to the sample for another preferred mode carrying out this invention.

FIG. 12 is a process flow chart example calculation of the electronic states of the charge carriers for another preferred mode carrying out this invention.

FIG. 13 is the data about ESR Signal intensity when micro wave power is increased.

FIG. 14 is the test sample for another preferred mode carrying out this invention.

FIG. 15 is the test sample of PEDOT: PSS for another preferred mode carrying out this invention.

FIG. 16 is a data of ESR signal about for another preferred mode carrying out this invention.

FIG. 17 is a data of ESR signal when the magnetic angle to the sample changed.

FIG. 18 is a schematic of molecular orientation of polyalkylthiophene in an FET analyzed by this invention.

FIG. 19 is actual sample2 of organic thin film device.

FIG. 20 is another sample2 of organic thin film device.

FIG. 21 is ESR signal data dependent hole buffer layer of sample2 measured by another preferred mode carrying out this invention.

FIG. 22 is electric characteristic data of sample2

FIG. 23 is energy level and states of charge carrier measured by another preferred mode carrying out this invention.

EXPLANATION OF SIGN

-   50 substrate -   52 organic thin film layers -   54 and 56 negative electrodes -   58 positive electrode -   60 and 62 wirings -   100 sample tube -   120 sample for measurement -   130 connected wiring -   140 joining terminal -   200 cavity -   205 optical penetration window -   210 electromagnet -   230 microwave bridge -   240 circulator -   250 phase sensitive detector -   260 signal analyzer -   300 light receiving/emitting device -   310 electric characteristic measuring device -   400 controller -   420 accumulation charge career information calculation means -   440 partial function electron spin resonance signal extraction means -   500 rotation belt

PREFERRED MODE FOR CARRYING OUT THE INVENTION

FIG. 1 is a block diagram of a preferred mode for carrying out this invention. As FIG. 1 the electron spin measuring device of this invention comprises cavity (200) in which the optical penetration window (205) that can transmit substantially without influence of dispersion by refraction ratio from visible ray to infrared rays. It is possible to irradiate light to the sample and or, to detect the light which irradiate from the sample, electromagnet (210), electro-magnet power source (220), microwave bridge (230), circulator (240), phase sensitive detector (250), signal analyzer (260), and light receiving/emitting device (300) that is used for device evaluation. For the sample device, electric characteristic measuring device (310) operates. For the sample organic solar battery, the electric characteristic measuring device (310) operates while semi-solar light is irradiating the sample. The lifetime of the sample, while semi-solar is irradiating to the sample, is possible to measure by controlling the electric characteristic measuring device (310) 

1. An electron spin measuring device comprising: a tube wherein a test sample is inserted, a cavity wherein the tube is inserted, an electric measuring device of the organic thin film device, the wire that is connected the test sample and the electric measuring device, and a light emitting and measuring light device that irradiates light to the sample and or measure light from the organic thin film device, the electron spin measuring monitors for observing the absorption as the field is changed, while irradiating the micro wave in which contain Zeeman energy division frequency, to the cavity, and measuring the energy level transition that occurs when the electron spin direction is reversed.
 2. The electron spin measuring device in claim 1, wherein further comprising: the control unit that is connected to the light emitting and measuring light device, and the device which output the data that contain the characteristic of the organic thin film device and the electron spin resonance of charge carrier on the same time.
 3. The electron spin measuring device of the organic thin film device in claim 1, wherein further comprising: the window that penetrates the light irradiation and the sample can be detected in the wavelength band of the far-red light.
 4. The cavity and the sample tube: because it assumes the direction of the magnetic field and the direction of the light irradiation to be arbitrary and changeable possible to respect of the sample located in the sample jurisdiction, electron spin measuring device of organic thin film element that makes the sample jurisdiction sample point object, and has means to become rotatable independently respectively like concentric circle described in claim
 1. 5. The cavity in claim 1 installs the rotation belt wherein the rotation belt has a light receiving/emitting device to be rotatable with the cavity to outer of the cavity, and the rotation belt is independence in rotatable respectively like the concentric circle with the sample tube described in claim
 1. 6. The rotation belt in claim 5 is made of non-magnetic material, and contained the gear type rotation mechanism.
 7. The electron spin measuring device of the organic thin film element in claim 1, wherein further comprising: moving means wherein the sample is located to adjust the direction of luminescence from the sample to adjust the direction of the magnetic field and the direction of the light irradiation.
 8. The light receiving/emitting device uses the optical fiber described in claim
 1. 9. Electron spin measuring device of organic thin film element that has partial function electron spin resonance signal extraction means to compare electron spin resonance signals of two or more samples and to extract only electron spin resonance signal in specific functional portion further described in claim
 6. 10. The wavelength of the micro wave is 3 cm (The frequency is X band of 10 GHz belt), the strength of the micro wave is from 0.01 mW to 2 mW, and the strength of modulation magnetic fields is below 0.1 Tesla more than 0.001 Tesla an electron spin measuring device from claim
 1. 11. Electron spin measuring device of organic thin film device described in claim 8 wherein it provided with accumulated charge carrier information calculation means to calculate generation part, charge carrier kind, and accumulated charge carrier density of charge carriers from spectrum divergence factor g value, linewidth ΔH, and electron spin resonance signal shape obtained from electron spin resonance signal further.
 12. An electron spin measuring method of organic thin film device containing: putting organic thin film on the same substrate or other substrates at least two test samples including the 2nd test sample that excludes an organic function thin films from the 1st test sample, and concerned that consists of organic thin film device and them, sealing the tube by the vacuum or specific gas, inserting the tube in cavity, measuring the electron spin resonance of the unpaired electron moving the 1st test sample and 2nd test sample while sweeping the magnetic field, extracting the electron spin resonance of the organic thin film device by substrate the signal of the 1st test sample device and 2nd test sample.
 13. The organic thin film device is the organic solar cell at least semiconductor comprising: at least P type or N type semiconductor, the cavity has window that pass the sun spectrum irradiation light by the solar simulator.
 14. The organic thin film device is electro luminescence comprising: comprising organic emitting layer wherein the layer is P type or N type semiconductor, the cavity has window that pass the emitting light. 